Solidified and shelled alcohols

ABSTRACT

Alcohols effectively solidified by using various hydroxides in combination with different cellulose compounds, and also, alcohols effectively solidified by using various cyanoacrylate monomers in combination with different cellulose compounds. The cyanoacrylate reactions complete very rapidly in seconds and generally release large amounts of heat. Suitable additives are added to slow down the reactions for gradual heat dissipation and easy manipulation. The alcohol liquids can be solidified as well. Solid alcohol blocks and alcohol gels may be shelled by dipping into cyanoacrylate and coating them with a cyanoacrylate shell for long term storage.

FIELD OF THE INVENTION

This invention relates to solidified and “shelled alcohols.” Thisinvention relates to jellification of alcohols utilizing (first method)hydroxide solution and modified cellulose; and also utilizing (secondmethod) cyanoacrylates and modified cellulose. It relates to the dippingof alcohol compositions, resulting from the application of the first orsecond methods, into cyanoacrylate solvent to form a shell on thealcohol composition, to prevent evaporation. It relates to the use ofcompounds with an acetone structure to slow down the rare of the second(cyanoacrylate method. It also relates to these alcohol compositions ascarriers for chelated metals complexes, which these metal complexes mayburn with different colored flames; ans as carriers for differentincenses. This invention also relates to condensed fuels for cooking andheating. It also relates to solid transparent plastic.

This invention relates to gelled organic liquids where the structure ofthe organic liquids have been changed from free flowing liquids toliquids that do not flow and are considered solids under ASTM D4359-84.More particularly, this invention relates to organic liquids that can beused as fuels that are gelled to the extent that they are considered tobe solids under ASTM D4359-84.

BACKGROUND OF THE INVENTION

Polymer gels consist of cross-linked macromolecules that form a threedimensional network in which solvent molecules are absorbed by osmoticforces.

There are several advantages of absorbing organic liquids into gels. Forexample, the liquid can be transformed into a soft solid by entrappinginto a three dimensional matrix of a gel. Soft solids have typicalproperties that are intermediate between solids and liquids. Forexample, gelled organic liquids can have a high viscosity as well as afinite deformation modulus. It is easier to apply an organic liquid to asurface in a thickened condition rather than as a free flowing liquid.This is particularly the case with vertical surfaces. Products that areusefully thickened include organic based paints, paint and corrosionremovers, nail polish removers, pastes, lotions, creams, salves,shampoos, household and commercial cleaners, oil drilling fluids, fuelsand charcoal lighter fluids.

Gelled fuels are particularly useful for cooking and chafing dishes.They are easier and safer to transport and are more effective owing tothe slower diffusive release of the fuel from the gelled matrix. Suchgelled fuels typically contain an alcohol, usually methanol or ethanolas the fuel, which may be mixed with other C1 to C6 alcohols. It isdesirable to gel the fuel in such a manner that it does not separatefrom the matrix on standing or on application of pressure. There are yetmany other uses for thickened organic liquids. When the organic liquidis gelled, it will also have a significantly reduced rate ofevaporation. Gelled fuels in transport vehicles reduce the risk of firein an accident.

Jellifying organic solvents has proceeded in different ways. In somecases, alcohol molecule were retained inside some salt precipitation, inother cases, nitrocellulose were used for holding the organic solvents.More recently, a long chain anionic polymer such as polyacrylic acidpolymer have been used to crosslink the organic solvent molecule.

One motivation for jellifying organic solvents, for example, is that itis easier to apply tan organic solvents to a surface in a thickened formrather than as a free flowing liquid. This is particularly true withrespect to a vertical surface, for example, a wall. There are many otheruses for thickened organic solvents. Paint, corrosion remover, householdcleaner and charcoal lighter fluids include some of the areas for athickened organic solvent.

The gelled fuel, moreover, will retard the speed of evaporation andincrease the effectiveness of burning. The gelled fuel also acts todecrease the amount of organic solvent in air. It has been found toreduce accidental fire hazards because, for example, the bulk of fuelwill be inside the matrix instead of fully exposed and available to theflame, being easier to put out.

A problem arises in applying the gels, is the lack of sufficientsubstantive structure (hardness), i.e., the gel preferably needs a veryhigh viscosity. of the gel itself. A solidified alcohol would tend tosolve this problem.

Gelled fuels may be used for cooking and heating foods. A difficulty mayarise when a soft gel melts during the burning process. For indoorcooking it is preferred to have smoke-free fuels such as methanol andethanol. Again, a solidified alcohol would tend to solve this problem.

Fuels to be effectively used without a wick to deliver the fuel to aburn surface must be gelled. The fuel must not separate from the gel onstanding or upon the application of pressure. The primary reason issafety. If a gelled fuel is classified as a solid under ASTM D4359-84 itwill be subject to less vigorous regulations for transport and storage.A solidified gel would tend to solve this problem.

Alcohol based gels have been formed by different gelling agents. In U.S.Pat. No. 3,148,958 there is disclosed the gelling of an alcohol fuelthrough the use of carboxy vinyl polymers neutralized with a weak aminebase. In U.S. Pat. No. 3,214,252 there is disclosed the use ofolefin-maleic anhydride copolymers as gelling agents for alcohols. U.S.Pat. No. 3,754,877 discloses the use of olefin modified hydroxyl alkylcellulose as the gelling agent. U.S. Pat. No. 3,759,674 discloses thedispersions of ethylene-acrylic acid copolymers and amine emulsifiers inwater, which form gels when mixed with alcohols. U.S. Pat. No. 4,261,700and U.S. Pat. No. 4,365,971 each disclose the use of a Carbopol 934ethylene acrylic acid copolymer gelling agent for an alcohol fuel. TheCarbopol 934 is neutralized to form the gel using a weak amine base.U.S. Pat. No. 4,436,525 discloses the gelling of a 3:1 mixture of methylalcohol and isopropyl alcohol with a fatty acid soap and sodiumhydroxide. U.S. Pat. No. 5,641,890 discloses the use of an amineneutralized anionic polymer such as Carbopol 676 along with anamphoteric rheological additive such as dispersed alumina for gellingalcohol. U.S. Pat. No. 6,794,467 B2 discloses a process for thepreparation of polymeric absorbents useful for gelling organic liquids.

In U.S. Pat. No. 4,536,188, the incorporation of alcohol soluble metalcompounds to increase the visibility of flame was disclosed.

BRIEF SUMMARY OF THE INVENTION

This invention comprises alcohols effectively solidified by usingvarious hydroxides in combination with different cellulose compounds,and also, alcohols effectively solidified by using various cyanoacrylatemonomers in combination with different cellulose compounds. Thecyanoacrylate reactions complete very rapidly in seconds and generallyreleased with large amounts of heat. Suitable additives are added toslow down the reactions for gradual heat dissipation and easymanipulation. The alcohol liquids can be solidified as well. Solidalcohol blocks and alcohol gels may be shelled by dipping intocyanoacrylate and coating them with a cyanoacrylate shell for long termstorage.

The invention comprises solid alcohols and shelled alcohols. A firstalcohol composition solid is formed from a first reaction of arelatively small amount of sodium hydroxide or potassium hydroxide mixedwith a suspension solution of modified cellulose polymer and an alcoholat low temperature.

A second alcohol composition solid may be formed from a second reactionof cyanoacrylate monomer mixed with a suspension solution of modifiedcellulose polymer and alcohol at low temperature. A third alcoholcomposition solid may be formed from a third reaction which is thesecond reaction modified with the addition ofacetone-structure-containing compounds in the cyanoacrylate solvent,which are mixed with a solution of a suspension of modified cellulosepolymer and alcohol, at room temperature. Acetone structure-containingcompounds may be selected from a group including pyridine, borate,bromocresol purple, amidoblack, and dimethylsulfoxide and other similarcompounds containing acetone—like (CH3C═O) structure.

The invention further comprises shelled alcohols: a coated, or shelled,alcohol-containing gel formed by dipping an alcohol-containing gel in acyanoacrylate. The coating forms a relatively impervious shell, i.e.,impervious to the evaporation of alcohol molecules. Wax granules may beadded to the various reactions for forming the different solids in orderto improve the smoothness of the respective solid's surface.

This invention further comprises organic liquids that can be used asfuels that are gelled to the extent that they are considered to besolids under ASTM D4359-84.

DETAILED DESCRIPTION OF THE INVENTION

The invention comprises solid alcohols and shelled (coated) alcohols.

The present invention is directed to produce solids and/or gels. Thisinvention is directed to gelled organic liquids where the structure ofthe organic liquids have been changed from free flowing liquids toliquids that do not flow and are considered solids under ASTM D4359-84.

This invention comprises a very rigid polymer matrix and a highly stickygel shelled with the hard polymer matrix. This invention comprises ashelled alcohol gel or shelled alcohol solid which allows for storage ofchemical energy for very long period, with almost no evaporation of thealcohol gel or alcohol solid.

Solid or gelled alcohol compositions are formed by a first method, asecond method, and a third method. The shelled alcohols are formed by afourth method. In a first aspect of the invention, a solid or gelledalcohols composition is formed by mixing an alcohol, a modifiedcellulose solution suspension, and a weak solution of an alkali such assodium or potassium hydroxide.

In a second aspect of the invention, a solid or gelled alcoholcompositions is formed from a first reaction of cyanoacrylate monomermixed with a suspension solution of modified cellulose polymer andalcohol at low temperature.

In a third aspect of the invention, which is a variation of the secondaspect, a solid or gelled alcohol composition is formed from a reactionthat also includes the addition of acetone-structure-containingcompounds to the cyanoacrylate solvent, which is then mixed with asolution of a suspension of modified cellulose polymer and alcohol, atroom temperature. Acetone (CH3C═OCH3) structure (CH3C═O) containingcompounds include pyridine, borate, bromocresol purple, amidoblack, anddimethylsulfoxide.

In a first preferred embodiment of this invention, a first alcoholcomposition is formed, comprising an alcohol with at least one carbonatom and containing a suspension of modified cellulose of about 1 to 13percent by weight which has been cross-linked by a metal hydroxide,where the metal hydroxide is about 2.5×10−5 to 1.25×10−3 percent byweight, and distilled water of about 2 to 5 percent by weight, where thedistilled water increases the transparency of the alcohol gel.

An alcohol selected for use in the reactions herein includes simplealcohols (such as methyl alcohol, ethyl alcohol, propyl alcohol,isopropyl alcohol, butyl alcohol, pentyl alcohol, isobutyl alcohol,allyl alcohol, furfural), cyclic alcohols (cyclohexanol), aromatic ringcontaining alcohols (benzyl alcohol), diols (such as ethylene diols,propylene dials, butylene diols, diethylene glycol) and polyethyleneglycols.

The modified cellulose selected for use in the reactions herein includesmethyl cellulose and carboxyl cellulose.

The metal hydroxide selected for use in reactions herein includes sodiumhydroxide and potassium hydroxide.

The cyanoacrylates include all available cyanoacrylates includingcommonly used methyl cyanoacrylate and ethyl cyanoacrylates.

EXAMPLE 1

About 500 ml of methyl alcohol is mixed with a suspension solution ofmethyl cellulose which is 30 g, by weight (range: 5 g to 50 g,preferably 25 to 35 g) and reacted with sodium hydroxide, which is 0.01g by weight (range 0.01 to 0.2 g, preferably 0.01 to 0.5 g) and 10 ml ofdistilled water (range 10 ml to 20 ml, preferably 10 ml). Thetemperature of the reaction which produces this first alcoholcomposition is about 20° C. (range: 10° C. to 70° C., preferably 20°) ata pressure of about 1 atmosphere.

To reduce smokiness of the resultant alcohol gel fuel, a low orderalcohol, such as methanol or ethanol may be used.

In order to color the flame as the gelled/solid fuel burns, an agentwhich will burn with a color is added to the reaction which produces thegel/solid fuel. A metal atom carried in solution by a chelating agent,for example, ethylenediamminetetraacetate ion EDTA4. EDTA4-forms verystable complexes with most of the transition metals. This hexadentateligand forms very stable complexes (usually octahedral structures) withmost of the transition metals. The donor atoms in EDTA4-are the two Natoms, and the four, negatively charged O atoms.

EDTA-metal complexes will dissolve in an organic fluid and will burnwith the characteristic color of the metal atom in a flame.

EXAMPLE 2

To form a variation of the first alcohol composition which may burn witha colored flame, ethyl alcohol (500 ml), a relatively small amount of anEDTA-metal complex and a suspension of methyl cellulose (30 g) (range: 5g to 50 g, preferably 25 to 35 g) are mixed with potassium hydroxide(0.01 g) (range 0.01 to 0.2 g, preferably 0.01 to 0.5 g) and distilledwater (15 ml) (range: 10 ml to 20 ml water), which ingredients reactwith cross-linkages to form an alcohol gel in which the water acts toincrease the transparency of the alcohol gel. This first variationalcohol composition formation is carried out at a temperature of 20° C.,(range: 10° C. to 70° C., preferably 20°) and a pressure of about oneatmosphere.

In a second preferred embodiment of this invention, a second alcoholcomposition comprising an alcohol with at least one carbon atom andcontaining a suspension of modified cellulose of about 1 to 13 percentby weight which has been cross-linked a cyanoacrylate, where thecyanoacrylate to alcohol volume ratio is 1:1 with a with a range of 1:5to 5:1.

The mixing of alcohol and cyanoacrylate may be done with equal volume ofeach reagent. However in applications the alcohol/cyanoacrylate ratiosmay be varied in a range from 1:5 to 5:1 depending upon which alcohol orcyanoacrylate is used. The basic reaction rates may be controlled byutilizing low temperature and adding specific chemicals.

EXAMPLE 3

About 500 ml of ethyl alcohol is mixed with a suspension solution ofethyl cellulose which is about 30 g, by weight (range: 5 g to 50 g,preferably 25 to 35 g) and reacted with ethyl cyanoacrylate, which is inabout a 1:2 ratio by volume, i.e., 250 ml (with a range about 5:1 to 1:5by volume). The temperature of the reaction which produces this secondalcohol composition is about 10° C. (range: 1° C. to 15° C.) at apressure of about 1 atmosphere.

In a third preferred embodiment, the alcohol gel and the reaction may bemodified with the addition of acetone structure containing compounds incyanoacrylate solvent. The reaction of such solution with suspension ofmodified cellulose polymer and alcohol is then performed at roomtemperature. The reaction may be much slower and more easily controlled.The alcohol gel structure retains cross-linkage from the cyanoacrylatereacted more slowly the alcohol suspension of a modified cellulose.

Acetone structure containing compounds include the addition of thefollowing compounds: pyridine, borate, bromocresol purple, amidoblack,and dimethylsulfoxide and other similar compounds containingacetone-like

EXAMPLE 4

About 500 ml of methyl alcohol is mixed with a suspension solution ofcarboxyl cellulose, which is about 30 g, by weight (range: 5 g to 50 g,preferably 25 to 35 g) and reacted with methyl cyanoacrylate whichcontains a small amount of pyridine, which is in about a 1:1 ratio byvolume, i.e., 500 ml, (with a range about 5:1 to 1:5 by volume). Thetemperature of the reaction which produces this third alcoholcomposition is about 22° C. (preferably room temperature with somerange, about 5° C. to 70° C.) at a pressure of about 1 atmosphere.

The invention further comprises shelled alcohols, a coated, or shelled,alcohol-containing gel. Shelled alcohols are formed by dipping analcohol-containing solid or gel formed from the first method, the secondmethod or the third method into a cyanoacrylate monomer. Wax granules,dissolvable in a cyanoacrylate, may be added to the second or thirdreaction for forming the second solid in order to improve the smoothnessof the solid's surface.

Shelled, or coated, alcohols are formed by the method of dipping thesolid or gel from the first method, second method or third method intocyanoacrylate monomer. Reduced evaporation of alcohol from said alcoholsolid is achieved by said applied, relatively impervious, cyanoacrylateshell. The cyanoacrylate coating forms a relatively impervious shell,i.e., impervious to the evaporation of alcohol molecules.

The alcohols and the cyanoacrylates which may be used in these reactionshave already been listed above.

This invention may be applied toward solving some current problemsassociated with the use of gelled fuels. This invention tends to preventany substantial loss of solvent by evaporation after long term storage.The shelled alcohols of this invention provide methods and products forachieving this lowered evaporation rate since the cyanoacrylate providesa sealed shell covering which is relatively impervious to evaporatingalcohol molecules

This invention tends to solve the problem of lack of solidity of the gelby utilizing a solidified alcohol.

This invention tends to solve the problem when a soft gel melts duringthe burning process.

This invention tends to solve the problem of using a fuel to beeffectively used without a wick by delivering the fuel to a burnsurface. The fuel tends not to separate from the gel on standing or uponthe application of pressure since the alcohol solid fume may beclassified as a solid under ASTM D4359-84. It will consequently besubject to less vigorous regulations for transport and storage.

The solidified alcohols have a wide area of application. Threeparticular areas of usage are: a) as carriers for different incenses; b)as condensed fuels for cooking and heating; and c) as solid transparentplastic.

1. A first alcohol composition, comprising: an alcohol with at least onecarbon atom and containing a suspension of modified cellulose of about 1to 13 percent by weight which has been cross-linked by a metalhydroxide, where the metal hydroxide is about 2.5×10−5 to 1.25×10−3percent by weight, and distilled water of about 2 to 5 percent byweight, wherein the distilled water increases the transparency of saidalcohol composition.
 2. The composition of claim 1, further comprising:a metal atom carried in solution by a chelating agent wherein saidcomposition containing said metal complexes will burn with acharacteristic color of the metal atom in a flame.
 3. The composition ofclaim 2, further comprising: EDTA4-as said chelating agent.
 4. A methodfor forming a shell on an alcohol composition, comprising the steps of:dipping said alcohol composition into a solvent consisting essentiallyof cyanoacrylate monomer therein coating said alcohol composition withcyanoacrylate; forming an essentially cyanoacrylate shell on saidalcohol composition.
 5. A method for using a cyanoacrylate shell toreduce evaporation, comprising the steps of: applying said cyanoacrylateshell to an alcohol solid; reducing evaporation of alcohol from saidalcohol solid wherein said cyanoacrylate shell is relatively imperviousto the evaporation of alcohol molecules.
 6. A method for making a firstalcohol composition, comprising the steps of: providing a suspensionsolution of modified cellulose polymer and alcohol; mixing a metalhydroxide solution with said suspension solution; and adding distilledwater to add transparency of the gel.
 7. The method of claim 6, furthercomprising the steps of: selecting said alcohol from a group consistingof methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol,butyl alcohol, pentyl alcohol, hexanol, isobutyl alcohol, allyl alcohol,furfural, cyclohexanol, benzyl alcohol, ethylene diols, propylene diols,butylene diols, diethylene glycol, polyethylene glycols, and polyols. 8.The method of claim 7, further comprising the step of: selecting a loworder alcohol, said alcohol selected from the group consisting ofmethanol and ethanol wherein the smokiness of said alcohol composition,used as a fuel, may be reduced.
 9. The method of claim 6, furthercomprising the step of: selecting said modified cellulose polymer from agroup consisting of methyl cellulose polymer and carboxyl cellulosepolymer.
 10. The method of claim 6, further comprising the step of:producing said alcohol composition as a solid.
 11. The method of claim6, further comprising the step of: producing said alcohol composition asa gel.
 12. The method for of claim 6, further comprising the steps of:dipping said alcohol composition into a solvent consisting essentiallyof cyanoacrylate monomer therein coating said alcohol composition withcyanoacrylate; forming an essentially cyanoacrylate shell on saidalcohol composition.
 13. A second alcohol composition, comprising: analcohol with at least one carbon atom; a modified cellulose of about 1to 13 percent by weight which has been cross-linked; a cyanoacrylate,wherein the cyanoacrylate to alcohol volume ratio is 1:1, with a ratiorange of 1:5 to 5:1 by volume.
 14. A method for making a second alcoholcomposition, comprising the steps of: providing a suspension solution ofmodified cellulose polymer and alcohol; mixing cyanoacrylate monomersolvent with said suspension solution; slowing rate of a reaction ofsaid cyanoacrylate and said suspension solution by maintaining a lowtemperature.
 15. The method of claim 14, further comprising the step of:selecting said alcohol from a group consisting of methyl alcohol, ethylalcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, pentylalcohol, hexanol, isobutyl alcohol, allyl alcohol, furfural,cyclohexanol, benzyl alcohol, ethylene diols, propylene diols, butylenediols, diethylene glycol, polyethylene glycols, and polyols.
 16. Themethod of claim 14, further comprising the step of: selecting saidcyanoacrylate from a group consisting of methyl cyanoacrylates and ethylcyanoacrylates.
 17. The method of claim 14, further comprising the stepof: selecting said cellulose polymer from a group consisting of methylcellulose and carboxyl cellulose.
 18. The method of claim 14, furthercomprising the step of: producing said alcohol composition as awater-free alcohol gel.
 19. The method of claim 14, further comprisingthe step of producing said alcohol composition as a solid.
 20. Themethod of claim 19, further comprising the step of: adding dissolvablewax granules to said cyanoacrylate solvent wherein said solid forms witha smoother surface.
 21. The method of claim 14, further comprising thesteps of: dipping said alcohol composition into a solvent ofcyanoacrylate monomer therein coating said alcohol composition withcyanoacrylate; and forming a cyanoacrylate shell on said alcoholcomposition.
 22. A method for making a third alcohol composition,further comprising the steps of: providing a suspension solution of amodified cellulose polymer and an alcohol; mixing a cyanoacrylatemonomer solvent with said suspension solution; slowing rate of areaction of said cyanoacrylate and said suspension solution with theaddition of at least one acetone-structure-containing compound in saidcyanoacrylate monomer solvent wherein said reaction may be performed atroom temperature.
 23. The method of claim 22, further comprising thestep of: producing said alcohol composition as a water-free alcohol gel.24. The method of claim 22, further comprising the step of: producingsaid alcohol composition as a solid.
 25. The method of claim 22, furthercomprising the steps of: adding dissolvable wax granules to saidcyanoacrylate solvent wherein said solid forms with a smoother surface.26. The method of claim 22, further comprising the steps of: dippingsaid alcohol composition into a solvent consisting essentially ofcyanoacrylate monomer therein coating said alcohol composition withcyanoacrylate; forming an essentially cyanoacrylate shell on saidalcohol composition.
 27. The method of claim 22, further comprising thestep of: selecting said at least one acetone-structure-containingcompound from a group consisting of: pyridine, borate, bromocresolpurple, amidoblack, and dimethylsulfoxide.
 28. The method of claim 22,further comprising the step of: selecting said alcohol from a groupconsisting of methyl alcohol, ethyl alcohol, propyl alcohol, isopropylalcohol, butyl alcohol, pentyl alcohol, hexanol, isobutyl alcohol, allylalcohol, furfural, cyclohexanol, benzyl alcohol, ethylene diols,propylene diols, butylene diols, diethylene glycol, polyethyleneglycols, and polyols.
 29. The method of claim 22, further comprising thestep of: selecting said cyanoacrylate from a group consisting of methylcyanoacrylates and ethyl cyanoacrylates.
 30. The method of claim 22,further comprising the step of: electing said cellulose polymer from agroup consisting of methyl cellulose and carboxyl cellulose.
 31. Themethod of claim 22, further comprising the step of: producing saidalcohol composition as a water-free alcohol gel.
 32. The method of claim22, further comprising the step of: producing said alcohol compositionas a solid.
 33. The method of claim 32, further comprising the step of:adding dissolvable wax granules to said cyanoacrylate solvent whereinsaid solid forms with a smoother surface.
 34. The method for of claim22, further comprising the steps of: dipping said alcohol compositioninto a solvent consisting essentially of cyanoacrylate monomer thereincoating said alcohol composition with cyanoacrylate; forming anessentially cyanoacrylate shell on said alcohol composition.
 35. Amethod for making a alcohol composition which may burn with a coloredflame, comprising the steps of: selecting an alcohol dissolvablechelating agent; forming a metal complex with a metal atom; dissolvingsaid metal complex in said alcohol; and reacting said alcohol to form acomposition chosen from the group consisting of a gel and a solidwhereby said composition containing said metal complexes may burn with acharacteristic color of the metal atom in a flame.
 36. The method ofclaim 33, further comprising the step of: selecting
 37. EDTA4-as saidchelating agent.